Ultraviolet holdback of nonsilver photosensitive systems by incorporating therein certain organic additives

ABSTRACT

Ultraviolet holdback of non-silver photosensitive compositions such as those described in U.S. Pat. Nos. 3,042,517 to 3,042,519 and similar non-silver free-radical compositions, is improved by the addition thereto of certain aromatic compounds, namely: aromatic heterocyclic compounds containing nitrogen as part of the ring systems, quinone compounds, pyrazolones, aromatic diamines, and aromatic esters of acetic acid.

United States Patent [191 Hazy et al.

[ 5] Dec. 2, 1975 1 ULTRAVIOLET HOLDBACK OF NONSILVER PHOTOSENSITIVESYSTEMS BY INCORPORATING TI'IEREIN CERTAIN ORGANIC ADDITIVES [75]Inventors: Andrew C. Hazy, Mentor; John E.

Shirey, Bedford; Lothar Ramins, Middlefield, all of Ohio [73] Assignee:Horizons Incorporated a division of Horizons Research Incorporated,Cleveland, Ohio 221 Filed Jan. 31, 1973 211 Appl. No.: 328,495

[52] US. Cl 96/90 R; 96/115 P [51] Int. Cl. G03C 1/52 [58] Field ofSearch 96/90 R, 115 P, 88

[56] References Cited UNITED STATES PATENTS 3,351,467 11/1967 Sprague etal. 96/90 3,502,476 3/1970 Itano et al 96/90 3,527,639 9/1970 Moraw 6/903,600,179 8/1971 Yamada ct al 96/90 3,620,748 11/1971 Fichter 96/903,790,376 2/1974 Hashine et al. 96/90 Primary Examinen-Won H. Louie, Jr.Attorney, Agent, or Firm-Lawrence 1. Field [57] ABSTRACT 8 .Claims, NoDrawings ULTRAVIOLET HOLDBACK or NONSILVER PHOTOSENSITIVE SYSTEMS BYINCORPORATING THEREIN CERTAIN ORGANIC ADDITIVES i This invention relatesto photosensitive compositions and to photosensitive films based on suchcompositions. More particularly, it relates to improved ultravioletholdback characteristics obtained from such photo- The importance ofthis invention will be apparent from the fact that in a significantportion of the photographic processing requiring the need forduplicationof information that may be available from a negative taken in a camera,in which relatively large numbers of such duplicates are required,ultraviolet light sources are commonly used in the printers involved insuch duplication in view of the high density of illumination that can bepacked in the small space in contradistinction to substantially lowerlevels of illumination that may be provided by visible light sources.Since ultraviolet is the commonly used source of illumination forduplication purposes and since duplicates may be made from duplicates,the sensitometric properties of the photographic system in theultraviolet are important and particularly with regard to the amount ofoptical ultraviolet density that can be achieved in the material onsuitable exposure to ultraviolet light. Intermediate masters exhibitingsuch high optical density in the image area, even though the density inthe visible may be very low, are 40 then suitable for use as stencils toenable one to copy the information onto a material which again willrequire the use of ultraviolet light for exposure purposes but in whichthe visible density isvery high. In reality, this is a process ofmultigeneration and the improved ultraviolet 'holdback described in thisspecification is of fundamental importance in order to achieve thedesign purpose.

Compounds useful in the practice of this invention fit into thefollowing general classificationsz aromatic or partially aromaticheterocyclic materials containing nitrogen as part of the ring system,quinone compounds, aromatic diamines, and aromatic esters of aceticacid.

The photosensitive compositions to which the present invention isparticularly applicable are non-silver photosensitive compositionscomprising an N-vinyl color forming compound and an activator, usuallyan organic halogen compound or a sulfur containing compound as describedin the following U.S. patents, among others:

N-Vinyl Color Forming Compounds U.S. Pat. Nos. 3,042,517; 3,042,5183,042,519; 3,056,673

Organic Halogen Activator Compounds U.S. Pat. Nos. 3,042,515; 3,147,117

Sulfur Containing Activator Compounds U.S. Pat. No. 3,285,744 V Sulfurand Halogen Containing Activator Compounds U.S. Pat. No. 3,113,024

The disclosure of said patents are intended to be incorporated herein byreference.

The compounds enumerated below are representativeofspecificcompoundswithin the above classes and are intended to beillustrative and are not to be considered a complete listing of all'ofthose which are suitable for the present invention:

1. N-Vinyl Color Forming Compounds The N-vinyl color forming compoundswhich are utilized in the photosensitive compositions of this inventionare those described in U.S. Pat. Nos. 3,052,517; 3,042,518; 3,042,519;and 3,056,673, among others. Suitable compounds include:N-vinyl-carbazole, N- vinylphenyl-a-naphthylamine, N-vinylpyrrolidone,N- vinylsuccinimide, N-vinylacetanilide, N-vinylphenylacetamide,Nvinylmethylacetamide, and N- vinyldiglycolylimide.

. 2. Activators a. Organic Halogen Compounds The organic halogencompounds which are useful in the light sensitive compositions of thisinvention are those represented by the general formula AC-X;, wherein Arepresents a monovalent radical which may be halogen (Cl, Br or I), H,alkyl, substituted alkyl including halogen substituted alkyl, aryl,substituted aryl, aroyl, and arylalkyl and wherein each X represents ahalogen atom which may be either chlorine, bromine or iodine, it beingunderstood that not all of the X atoms need be alike. Preferredcompounds are halogen substituted alkanes, e.g. CBr CHI C HBr CI etc.,and a,a,a-tribromoacetophenoner b. Sulfur Containing Compounds Thesulfur containing compounds which are utilized in the photosensitivecompositions of the present invention are those represented by eitherthe formula R-SH or the formula R-S-SR wherein each R represents an arylor heterocyclic ring. Suitable compounds includeZ-mercaptobenzothiazole, S-methoxy- Z-mercaptobenzothiazole, l-phenyl-S-me rcaptotetrazole andpentachlorobenzenethio-bis(dimethylthiocarbonyDdisulfide. c. Sulfur andHalogen Containing'Compounds Activator compounds containing both halogenand sulfur and which are suitable for the compositions of the presentinvention include the sulfonyl and sulfenyl halides described in U.S.Pat. No. 3,1 13,024, e.g., 2,4- dinitrobenzenesulfonyl chloride,p-chlorobenzenesulfonyl chloride, o-nitrobenzenesulfenyl chloride andpentachlorobenzenesulfenyl chloride.

3. Binder As described in the above noted patents, the photosensitivecompositions are preferably formulated with av film forming binder andare cast as a thin film from solution usually as a thin coating on asuitable substrate. Among the binders which can be used are solutions ofpolystyrene, copolymers of styrene and acrylonitrile, polyphenyleneoxide, polycarbonate, polyvinylbutyral, suitable combinations of theabove, and others such as those described in U.S. Pat. Nos. 3,100,703and 3,147,117. The compositions have been utilized without a binder, forexample, when imbibed in a paper or other porous substrate. a

4. Additional Constituents Manycompounds which have been added forspecific benefits to the aforementioned photosensitive compositions arefully described in the above noted patents, including compounds tosensitize the composi- 5. Organic Compounds Producing Imagery I-lavingImproved Ultraviolet l-loldback The organic compounds the addition ofwhich to the otherwise known photosensitive compositions producesimagery having improved ultraviolet holdback, the use of which comprisesthe present invention, are compounds found in the following generalclasses: aromatic or partially aromatic heterocyclic materialscontaining nitrogen as part of the ring system, quinone compounds,aromatic diamines, and aromatic esters of acetic acid. Examples ofheterocyclic materials which have been found suitable include: indole,quinoline, acridine, acridan, phenoxazine, quinazoline, phenazine and2-phenylindole. Quinone compounds which are useful for the presentinvention include: l-amino-4- hydroxy-9, 1 O-anthraquinone,1-amino-4-benzamido- 9,10-anthraquinone, 1,4-diamino-9,10-anthraquinone, l-amino-S -benzamido-9, lO-anthraquinone, l ,S-dibenz amido-9, l O-anthraquinone, 1,4-diamino-2,3-dichloro- 9,10-anthraquinone and2-amino-1,4-naphthoquinone. Suitable aromatic diamines include:o-phenylenediamine, p-phenylenediamine, N-phenyl-p-phenylenediamine,N-phenyl-o-phenylenediamine, and the like. Aromatic esters of aceticacid which are useful for the present invention include: phenyl acetate,o-methoxyphenyl acetate, 4-chlorophenyl acetate, 2,4- dichlorophenylacetate and 2,4-dimethoxyphenyl acetate- Proportions Suitableproportions of the subject U.V. holdback producing compounds range from0.02 part to up to 2 parts by weight of such compound, for each part byweight of the N-vinyl color forming compound in the composition anddepends to some extent on the solubility of the particular additive inthe binder-solvent used.

Base

The formulations employed in this invention can be applied to anysuitable substrate such as cellulose acetate, polyesters such aspolyethylene terephthalate as defined by the trade names Mylar (E.l.duPont) and Celanar (Celanese Corporation), paper, cloth, glass, etc.

. Fixing Fixing photosensitive compositions employed in this inventionafter exposure, is accomplished by heat or by solvent wash as describedin the prior art.

EXAMPLES The following examples are illustrative of the ways in whichthe compounds referred to in this invention were used and are notintended as limitative thereof.

' 2,6-di-t-butyl-p-cresol, 220 mg of triethylamine, and 10 EXAMPLE 1 Abinder solution was prepared by dissolving 10 g of polyvinylbutyral inml of methylene chloride, 25 ml of chlorobenzene and 5 ml oftriethylamine To 6 ml of this solution was added 285 mg ofN-vinylcarbazole, 700 mg of carbon tetrabromide, 50 mg of2,6-di-tbutyl-p-cresol and 10 mg of triphenyl stibene. The resultingsolution was coated 0.003 inch thick (wet) on a sheet of polyethyleneterephthalate and then dried at C for 30 seconds. This film was exposedto a high pressure mercury arc lamp and then fixed by heating to 160Cfor 2 minutes. No visible image was obtained, but image density overbase plus fog, as read through a 366 nm filter, was 0.63 density units.An otherwise identical film was prepared, except that 10 mg oflamino-5-benzamido-9,lO-ahthraquinone was added to the formulation.After identical exposure and processing, this film produced a visibledensity of only 0.04, while the net density at 366 nm was 0.97.

EXAMPLES 2 and 3 A film was prepared as described in Example 1 exceptthat mg of 4-amino-2,3-dimethyl-1-pheny1-3- pyrazolin-S-one was addedinstead of the 1-amino-5- benzamido-9,IO-anthraquinone. This filmproduced a net density of 0.20 (visible) and a net density of 2.24 whenread through a 366 nm filter. Another film was prepared using 100 mg of2-phenylindole as the additive and this film gave a net density of 1.40at 366 nm and only 0.07 in the visible.

EXAMPLE 4 A film was prepared from the following formulation: 285 mg ofN-vinylcarbazole, 700 mg of carbon tetrabromide, 50 mg of2,6-di-t-butyl-p-cresol, 220 mg of triethylamine, and 10 mg of triphenylstibene in'6 ml of a 10% solution of polyvinylpyrrolidone in 3:1methylene chloride-chlorobenzene. That solution was coated 0.003 inchthick (wet) on polyethylene terephthalate and the film was dried at 90Cfor 30 seconds. Exposure to a high pressure mercury arc lamp wasfollowed by fixing at C for 2 minutes. The net density (366 nm) producedwas 1.35. An otherwise identical film wasprepared with 100-mg of indoleas an additive and this film produced a net density of 1.72 afteridentical exposure and processing.

EXAMPLE 5-7 Films were prepared as described in Example 4 except thatthe additive for each film was different. A film containing 100 mg of2-phenylindole gave a net density of 1.57, a film with 100 mg ofacridine in it produced a net density of 1.50 and a film which contained100 mg of 4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one as theadditive gave a net density of 2.50. Exposure and processing wereidentical with that of Example 4.

EXAMPLES 9-11 A control film was prepared from 285 mg ofN-vinylcarbazole, 700 mg of carbon tetrabromide, 50 mg of mg oftriphenylstibene in 6 ml of a 10% solution of polyarylsulfone in 3:1methylene chloride-chlorobenzene. This film gave a net density (366 nm)of 1.38 and a visible net density of 0.05 after exposure and fixing asdescribed in Example 1. To this control formulation was added 10 mg of1-amino-5-benzamido-9,10-

anthraquinone' and the resulting film produe d a net density of 1.58(366 nm) "and 0.18 in the visible. A similar film was made from thecontrol formulation with 100 mg of Z-ph'enylin'drfleas the additive andthis film gave a net'density of 0.15."Whe'n the control formulation wastreated with 100 mg of 4-arnino-2,3-dimethyl-1-phenyl-3-pyrazolin-5=o'ne; the resulting *film' gave 2.56 net densityat 366 rim; with only 0.30 net visible density. I i 1 EXAMPLES 12-16 Thecontrol formulation'used for'examples 9- 11 was coated'from a solutionofp'oly'carbonate in 3:1 methylene chloride-chlorobenzene instead ofpolyarylsulfone. This solution produced a film which gave a net density(366 nm) of 1.74. Similar polycarbonate films were then prepared usingthe following additives: 1O

. EXAMPLES 21-43 mulation was used as a control anda series of organiccompounds-wereevaluate'd as additives, in 100 mg concentrations, to thecontr'olsThe list of materials and the results obtained from therespectivefilms' are shown in Table 1. It should be noted that many ofthe additives produced improved ultraviolet holdback withoutsignificantly increasing the visible density'so that these compositionsare particularly useful for the production of see-through masks.

TABLE I Effect of Additives on Ultraviolet (366 nm) Holdback Example netDensity net Density Numbers Additive (366 nm) (visible) j None (control)1.30 0.04 21 lndole 1.54 0.16

22 Quinoline 1.95 0.05 23 Acridine 1.49 '0. l 8 24 Acridan a 2.20 0.2425 1-Amino-4-hydroxy-9, 1 O-anthraquinone l .45 0.30 26 1,4-Diamino-9, lO-anthraquinone 1.69 none 27 1-Amino-4-benzamido-9, IO-anthraquinone1.60 none 28 l-Amino-S-benzamido-Q, IO-anthraquinone 1 .80 0.14 29 1,5-Dibenzamido-9, 1 O-anthraquinone 1.38 0.03 30 l,4-Diamino-2,3-dichloro-9,10-anthraquinone l .42 none 31 2-Amino-l,4-naphthoquinone 1 .46 0.07 32 Phenoxazine 1.52 0.08 3 3 Quinazoline1.60 0.04 34 Quinoxaline l .53 0.06 35 Phenazine 1.67 0.04 364-Amino-2,3-dimethyll -phenyl-3-pyrazolin-5 -one 1 .92 0.22 372,3-Dimethyl-4-dimethylamino-1-phenyl-3- pyrazolin-S-one 1.70 0.08 38 13-Diphenyl-5-pyrazolone 1 .54 0.10 39 Phenyl acetate 1.38 0.04 40o-Methoxyphenyl acetate 1.59 0.04 41 o-Phenylenediamine 1.50 0.02 42N-Phenyl-p-phenylenediamine l .40 0.08 43 Z-Phenylindole 1.76 0.22

EXAMPLE 44 mg of acridan gave net density 2.32 while 100 mg of acridangave 2.53 net density; 10 mg of l-amino-S-benzamido-9,IO-anthraquinonegave net density of 1.83; 100 mg of4-amino-2,3-dimethyl-1-phenyl-3-pyrazolin- 5-one produced 2.62 netdensity; 100 mg of 2- phenylindole gave a net density of 2.00.

EXAMPLES 17-20 A formulation composed of 285 mg of N-vinylcarbazole, 10mg of triphenyl stibene, 50 mg of 2,6-di-tbutyl-p-cresol, 700 mg ofcarbon tetrabromide, 220 mg of triethylamine and 6 ml of a 10% solutionof polystyrene in 3:2 toluene-methyl ethyl ketone was coated 0.003 inchthick (wet) on polyethylene terephthalate and dried at 90C for 30seconds. The resulting film was exposed and fixed as described inExample 1 and gave 1.76 net density at 366 nm. When this formulation wascoated with 100 mg of acridan as an additive, the resulting filmproduced net density of 2.40 after identical exposure and fixing.

Similarly, a film utilizing 100 mg of o-methoxyphenyl acetate as anadditive gave 2.01 net density; using 10 mg of quinoline gave a filmwhich produced 2.11 net density.

A film was coated on polyethylene terephthalate from a solutionconsisting of 285 mg of N-vinylcarbazole, mg ofZ-mercaptolbenzothiazole, 35 mg of carbon tetrabromide, 64 mg oftriethylamine, 1 cc of acetone and 6 cc of 18% polystyrene in 2:1toluene ethylene dichloride. The film was exposed as in example l andthen heated to C for 1 minute to produce 0.11 net density (visible) and1.85 net density at 366 nm. An otherwise identical film was prepared,except that 50 mg of phenoxazine was added. After identical exposure andprocessing, the film gave 0.11 density (visible) and 2.28 net density at366 nm.

EXAMPLE 45 7 We claim: 1. In a non-silver photosensitive compositioncomamino-4-hydroxy-9,lO-anthraquinone, 1-amino-4- benzamido-9, l-anthraquinone, 1,4-diamino-9, l 0-- prising: I anthraquinone, lamino--benzamido-9,l0- l. at least one N-vinyl amine compound whichforms r anthraquinone, l-5-dibenzamido-9, IO-anthraquia color whenexposed to. a dose of suitable radia- 5 none,l,4-diamino-2,3-dichloro-9,IO-anthraqui- -tion inthe presence of anactivator; none and Z-amino-l,4-naphthoquinone, phenylene 2. at leastonesuch activator for said color forming diamines and phenylacetates. -1 aN-vinyl amine compound, said activator being se- 2. The composition ofclaim 1 in which the proporlected from the group consisting of (a)organic l0 tiori of N-vinyl compound and the compound produchalogencompounds represented by the general formula QCX wherein Q represents amonovalent radical selected from the group consisting of Cl, Br,"l, H,alkyl, aryl, aroyl and arylalkyl, and each X is a halogen atom selectedfrom the group consisting of Cl, Br and l; (b) sulfur containing organiccompounds represented by the formula RSH or RSSR in which each Rrepresents an aryl or heterocyclic ring; and (c) sulfonyl and sulfenylhalides; the improvement of which consists in the incorporation in saidcomposition of 3. at least one organic compound which produces imageryhaving improved ultraviolet holdback said 8. A photographic elementcomprising a support and compound being selected from the group consistacoating thereon comprising the composition of claim ing of indole,quinoline, acridine, acridan, phenoxl. azine, quinazoline, phenazine,2-phenylindole, lv ing imagery with improved ultraviolet holdback isbetween about 5021 and 1:2.

3. The composition of claim 1 in which the N-vinyl compound isN-vinylcarbazole and the holdback compound is l -amino-5-benzamido-9, lO-anthraquinone.

4. The composition of claim 1 wherein the holdback compound is anindole.

5. The composition of claim 1 wherein the holdbac compound is ananthraquinone.

6. The composition of claim 1 wherein the holdback compound is an phenyldiamine.

7. The composition of claim 1 wherein the holdback compound is an phenylester of acetic acid.

1. IN A NON-SILVER PHOTOSENSITIVE COMPOSITION COMPRISING:
 1. AT LEASTONE N-VINYL AMINE COMPOUND WHICH FORMS A COLOR WHEN EXPOSED TO A DOSE OFSUITABLE RADIATION IN THE PRESENCE OF AN ACTIVATOR;
 2. AT LEAST ONE SUCHACTIVATOR FOR SAID COLOR FORMING N-VINYL AMINE COMPOUND, SAID ACTIVATORBEING SELECTED FROM THE GROUP CONSISTING OF (A) ORGANIC HALOGENCOMPOUNDS REPRESENTED BY THE GENERAL FORMULA 1-C-X3 WHEREIN Q REPRESENTSA MONOVALENT RADICAL SELECTED FROM THE GROUP CONSISTING OF CL, BR, I, H,ALKYL, ARYL, AROYL AND ARYLALKYL, AND EACH X IS A HALOGEN ATOM SELECTEDFROM THE GROUP CONSISTING OF CL, BR AND I; (B) SULFUR CONTAINING ORGANICCOMPOUNDS REPRESENTED BY THE FORMULA RSH OR RSSR IN WHICH EACH RREPRESENTS AN ARYL OR HETEROCYCLIC RING; AND (C) SULFONYL AND SULFENYLHALIDES; THE IMPROVEMENT OF WHICH CONSISTS IN THE INCORPORATION IN SAIDCOMPOSITION OF
 2. The composition of claim 1 in which the proportion ofN-vinyl compound and the compound producing imagery with improvedultraviolet holdback is between about 50:1 and 1:2.
 2. at least one suchactivator for said color forming N-vinyl amine compound, said activatorbeing selected from the group consisting of (a) organic halogencompounds represented by the general formula Q-C-X3 wherein Q representsa monovalent radical selected from the group consisting of Cl, Br, I, H,alkyl, aryl, aroyl and arylalkyl, and each X is a halogen atom selectedfrom the group consisting of Cl, Br and I; (b) sulfur containing organiccompounds represented by the formula RSH or RSSR in which each Rrepresents an aryl or heterocyclic ring; and (c) sulfonyl and sulfenylhalides; the improvement of which consists in the incorporation in saidcomposition of
 3. at least one organic compound which produces imageryhaving improved ultraviolet holdback said compound being selected fromthe group consisting of indole, quinoline, acridine, acridan,phenoxazine, quinazoline, phenazine, 2-phenylindole,1-amino-4-hydroxy-9,10-anthraquinone,1-amino-4-benzamido-9,10-anthraquinone, 1,4-diamino-9,10-anthraquinone,1-amino-5-benzamido-9,10-anthraquinone,1-5-dibenzamido-9,10-anthraquinone,1,4-diamino-2,3-dichloro-9,10-anthraquinone and2-amino-1,4-naphthoquinone, phenylene diamines and phenylacetates. 3.The composition of claim 1 in which the N-vinyl compound isN-vinylcarbazole and the holdback compound is1-amino-5-benzamido-9,10-anthraquinone.
 3. AT LEAST ONE ORGANIC COMPOUNDWHICH PRODUCES IMAGERY HAVING IMPROVED ULTRAVIOLET HOLDBACK SAIDCOMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF INDOLE, QUINOLINE,ACRIDINE, ACRIDAN, PHENOXAZOLINE, PHENAZINE, 2-PHENYLINDOLE,1-AMINO-4-HYDROXY-9,10ANTHRAQUINONE,1-AMINO-4-BENZAMIDO-9,10-ANTHRAQUINONE, 1,4-DIAMINO-9,10-ANTHRAQUINONE,1-AMINO-5-BENZAMIDO-9,10-ANTHRAQUINONE,1-5-DIBENZAMIDO-9,10ANTHRAQUINONE,1,4-DIAMINO-2,3-DICHLORO-9,10ANTHRAQUIONE AND2-AMINO-1,4-NAPHTHOQUINONE, PHENYLENE DIAMINES AND PHENYLACETATES. 4.The composition of claim 1 wherein the holdback compound is an indole.5. The composition of claim 1 wherein the holdback compound is ananthraquinone.
 6. The composition of claim 1 wherein the holdbackcompound is an phenyl diamine.
 7. The composition of claim 1 wherein theholdback compound is an phenyl ester of acetic acid.
 8. A photographicelement comprising a support and a coating thereon comprising thecomposition of claim 1.